System And Process For Removal Of Organic Carboxylates From Mono Ethylene Glycol (MEG) Water Streams By Acidification And Vaporation Under Vacuum

ABSTRACT

A system and method for removing organic carboxylates from a mono ethylene glycol (“MEG”) stream includes a reaction vessel; means for cooling and diluting the MEG stream being routed to the reaction vessel; means for acidifying the cooled and diluted MEG stream during its residence time within the reaction vessel; and means for removing an acetic-rich overhead stream from the reaction vessel. The acidification of the cooled and diluted MEG stream occurs under a vacuum. The reaction vessel may be located downstream of a calcium removal vessel and receive a filtered bottom stream from that vessel, or it may be a single reaction vessel that cycles between a calcium removal mode and an acetate removal mode, with the pressure of the single vessel being greater during the calcium removal mode than during the acetate removal mode.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application which claims priority toU.S. patent application Ser. No. 15/044,752, filed Feb. 16, 2016, whichwas a divisional application which claimed priority to U.S. patentapplication Ser. No. 14/051,138 filed on Oct. 10, 2013, both of whichare incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to systems and methods designed to treat monoethylene glycol (“MEG”) streams used in the oil and gas industry tocontrol hydrates formation in the production pipeline. Moreparticularly, the invention relates to systems and processes which allowfor removal of carboxylates from the MEG water stream of a MEGreclamation and regeneration package to reduce MEG losses.

In the oil and gas industry, dry (lean) MEG is injected into theproduction pipeline to control the formation of hydrates within theproduced stream. The MEG injection is part of a MEG loop of a gasproduction facility. The loop typically includes a reclamation andregeneration package to treat the wet (rich) MEG and reclaim as much MEGas possible for reinjection into the pipeline.

The formation waters and condensed waters, which arrive at the gasproduction facility along with the raw hydrocarbon products, containorganic acids. Because these organic acids are highly soluble inMEG-water mixtures, they tend to follow the MEG-water stream.Additionally, in order to protect production pipelines againstcorrosion, and to remove dissolved divalent cations from the MEG stream,the pH of the MEG-water in the pipeline is elevated by the addition ofbases such as sodium hydroxide. At elevated pH, the organic acids arepresent as a carboxylate salt (e.g., sodium acetate).

The low volatility of the carboxylate salts results in theiraccumulation in MEG process streams within the MEG loop. Thisaccumulation, in turn, results in increased viscosity and density,making the MEG streams more difficult to pump.

To control the carboxylate levels in the MEG loop, the carboxylate-richMEG is periodically discharged. However, this results in loss of MEGfrom the system and requires replacement to ensure the MEG inventory ofthe loop is maintained. Therefore, a need exists for systems andprocesses which control the carboxylate levels and reduce or eliminateMEG loss in the loop.

Carboxylate accumulation (either as the organic acid or as thecorresponding salt) is an issue for MEG reclamation and regenerationpackages due to the high solubility of these species in the water-MEGaqueous phase.

In order to minimize corrosion issues, the MEG Loop is operated atrelatively high pH whereby the carboxylic acids are presentpredominantly as the carboxylate salts which have low volatility and,thus, are not removed in the overheads (produced water) stream from theregenerators or reclaimers of the MEG Recovery Package. Their highsolubility in alkaline MEG solutions means that they do not precipitatewhen the pH is raised to remove the calcium, magnesium and otherdivalent cations.

Accumulation of acetates can lead to elevated density and viscosity inMEG streams which, in turn, lead to operational difficulties. Therefore,a need exists for a system and process to remove organic carboxylatesfrom the MEG water stream.

SUMMARY OF THE INVENTION

By employing a system and process made and practiced according to thisinvention, the problems discussed in the above background section areminimized because the acetate levels are controlled to a manageablelevel while MEG losses associated with the acetate removal process arekept to a minimum when compared to the alternative.

A system and process for removing organic carboxylates from a monoethylene glycol (“MEG”) stream includes a reaction vessel; means forcooling and diluting the MEG stream being routed to the reaction vessel;means for acidifying the cooled and diluted MEG stream during itsresidence time within the reaction vessel; and means for removing anacetate-rich overhead stream from the reaction vessel. The acidificationof the cooled and diluted MEG stream occurs under a vacuum.

The reaction vessel may be located downstream of a calcium removalvessel and receive a filtered bottom stream from that vessel, or it maybe a single reaction vessel that cycles between a calcium removal modeand an acetate removal mode, with the pressure of the single vesselbeing greater during the calcium removal mode than during the acetateremoval mode.

Preferably, the cooling and diluting means results in the incoming MEGstream to be 50 wt % MEG at a temperature in a range of 80° to 100° C.In the acetate removal mode, the pressure is sub-atmospheric, preferablyin a range of 0.1 to 0.3 bar. The acidifying means, which may behydrochloric acid, results in the cooled and diluted MEG stream duringits residence time within the reaction vessel to have a pH in a range of3.5 to 5.5.

Objects of the invention include providing a system and process which:(1) can be retrofitted into existing MEG loops; (2) controls and reducesthe amount of acetates in the MEG water stream; (3) extends the lengthof the production run; (4) reduces MEG loss; and (5) increases MEGrecovery for re-use.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a preferred embodiment of a system and process practicedaccording to this invention. A single reaction vessel is used for theremoval of calcium and carboxylates from a mono ethylene (MEG) waterstream. The reaction vessel swings or cycles between those two removalmodes. The acetate-rich overhead stream is routed directly to aknock-out drum.

FIG. 1B is another preferred embodiment of a system and processpracticed according to this invention. A single reaction vessel is usedfor the removal of calcium and carboxylates from a mono ethylene (MEG)water stream. Similar to FIG. 1A, the vessel cycles between those tworemoval modes. The acetate-rich overhead stream is routed directly to adistillation column where it is mixed with a MEG-water overhead streamfrom a reclaimer.

FIG. 2 is yet another preferred embodiment of a system and processpracticed according to this invention. One reaction vessel is used forthe removal of calcium from the MEG-water stream and another reactionvessel is used for the removal of carboxylates. The high pH streamgenerated in the calcium removal vessel is filtered to remove solids andthen treated with hydrochloric acid in the acetate removal vesseloperated at sub-atmospheric pressure.

FIGS. 3 to 7 show simulated results of a system and process madeaccording to FIGS. 1A, 1B and 2 for acetate removal from a modelsolution where solution pH was reduced to 4.5 prior to raisingtemperature and reducing pressure.

FIG. 3 is a graph of acetate removal as a function of temperature andpressure.

FIG. 4 is a graph of MEG losses in the reaction vessel overheads as afunction of temperature and pressure.

FIG. 5 is a graph of acetate removal against MEG loss for threetemperatures (80, 90 and 100° C.).

FIG. 6 is a graph of calculated MEG loss per kg of acetate rejected as afunction of operating pressure.

FIG. 7 is a graph of calculated acetate removed from the reaction vesselas a function of initial pH (3.5, 4.5, 5.5), temperature (60-100° C.),and operating pressure (0.1-0.3 bara).

FIG. 8 is schematic of an apparatus used to test preferred embodimentsof the system and process of this invention.

ELEMENTS AND ELEMENT NUMBERING USED IN THE DRAWING FIGURES

-   10 System-   11 Reaction vessel-   13 Incoming carboxylates-rich MEG stream-   15 Water stream-   17 Cooled and diluted MEG water stream-   19 Precipitating means-   21 Acidifying means-   23 Acetate-rich overhead stream-   25 Condensed acetate-rich overhead stream-   27 Calcium carbonates bottoms stream-   29 Filtered calcium carbonates bottoms stream-   101 Reactor vessel-   102 pH probe-   103 Dissolved oxygen probe-   104 Redox probe-   105 Electrical conductivity probe-   106 Stirrer-   107 Hot oil circulator bath and heater-   108 Condenser-   109 Distillate collection vessel-   110 Vacuum pump-   111 Pressure control valve-   112 Pressure transducer-   113 Oxygen-free nitrogen supply

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A system and process made and practiced according to this inventionallows a target salt (in this case acetate) to accumulate in a reactionvessel and then removes the acetate from a concentrated liquor withinthe reaction vessel, thereby keeping vessel site and inventory to aminimum.

Referring to the drawings and first to FIGS. 1A and B, a system 10 forremoving organic carboxylates like acetates from a MEG water streamincludes a reaction vessel 11 as part of the MEG loop of a MEGreclamation and regeneration package. The MEG reclamation unit (notshown) is typically operated at a temperature in a range of about120°-140° C. and at sub-atmospheric pressure (about 0.1-0.3 bara). Therecycle loop within the reclamation unit is operated at elevatedpressure (about 4 bar). The reaction vessel 11 is closely coupled to therecycle loop of the package.

The incoming carboxylate-rich MEG stream 13 is typically at 80-90 wt %MEG and high ph (>9.5). The incoming MEG stream 13 is cooled and dilutedwith water 15 to yield a cooled and diluted MEG water stream 17 whichenters and resides within reaction vessel 11 as a MEG water mixture. Thecooled and diluted MEG stream 17 is preferably at a temperature of about80-100° C. and 50 wt % MEG.

The reaction vessel 11 can be switched between a calcium removal mode(high pH, atmospheric pressure) and an acetate removal mode (low pH,sub-ambient pressure). The frequency of calcium removal cycles andacetate removal cycles can be varied to control the levels of calciumand organic acids in the MEG loop depending on the composition of theMEG feed entering the MEG regeneration package.

When reaction vessel 11 is in a calcium removal mode or cycle, thevessel 11 operates at atmospheric pressure and removes calcium and otherdivalent cations from the incoming MEG water stream by elevating pH.Precipitating means 19 such as sodium or potassium carbonate or sodiumor potassium hydroxide are introduced to the reaction vessel 11. Saltsresiding in the MEG water mixture—such as calcium chloride and,commonly, lesser amounts of other divalent salts like magnesium, bariumand strontium chlorides—react with the precipitant agent and precipitateout of the MEG water mixture as solid crystals. The solid crystals areremoved as a bottom stream 27.

When reaction vessel 11 is in an acetate removal mode, the vessel 11operates under a vacuum (preferably in a range of about 0.1-0.3 bar) andremoves carboxylates by lowering pH (preferably in a range of about3.5-5.5). The stream 17 is acidified within the reaction vessel 11 usingacidifying means 21 such as hydrochloric acid (e.g., 30 w % HCl inwater) to achieve a pH in a range of about 3.5-5.5. The pressure inreaction vessel 11 is then reduced to 0.1-0.3 bar and acetates areevolved along with water, some carbon dioxide and some MEG. Means wellknown in the art are employed to remove the acetate-rich overhead stream23 from the vessel 11.

The composition of the overhead stream 23 from the reaction vessel 11 isprimarily a function of temperature and pressure (see FIGS. 3 & 4).Ideally, the overhead stream 23 contains the maximum quantity of aceticacid and a minimum quantity of MEG. The results reported below in FIGS.3 & 4 can be applied to determine an optimum initial pH, temperature andpressure regime whereby the maximum yield of acetic acid is combinedwith a reduced yield of MEG in the stream 23.

In the system of FIG. 1A, the overhead stream 23 is condensed and thecondensed stream 25 (low pH<3) may be routed to water treatmentequipment or neutralized in a knock-out drum. In the system of FIG. 1B,the overhead stream 23 is condensed and the condense stream 25 is routeddirectly to the distillation column where it is mixed with a MEG-wateroverhead stream from the reclaimer. The acetates partition between theaqueous phase (produced water) and the lean MEG phase. Routineexperimentation can be used to determine the partitioning of acetic acidbetween water and lean MEG to determine the preferred routing of aceticacid-MEG-water stream from the acetate removal process.

Referring now to FIG. 2, separate vessels 31, 33 are used for calciumremoval and carboxylates removal, respectively. During simultaneousproduction of calcium and carboxylic acids the calcium (and otherdivalent cations) are precipitated in vessel 31 at approximately 80° C.and 1.0 bar by raising the pH using precipitating means 19 and filteringthe resulting calcium carbonates stream 27. The centrate/filtrate steam29 is acidified using acidifying means 21 at 80-100° C. and atsub-atmospheric pressure (about 0.1 to 0.3 bar) in vessel 33 to removethe organic acids and water as an overhead stream 23. The calcium-freeand organic acid-free MEG can be returned to the production process.

However, the same calcium removal process as that described for vessel11 (see FIGS. 1A and 1B) is employed within vessel 31, as is the sameacetate removal process for vessel 33.

Simulated Results

Simulated results were obtained employing OLI STREAM ANALYZER™ software(OLI Systems, Inc., Cedar Knolls, N.J. A model feed representing a highpH, 50% MEG solution with 3 wt % dissolved sodium acetate and excesssodium hydroxide and sodium bicarbonate was reacted with hydrochloricacid (as HCl) to reduce the pH to 3.5-5.5. The temperature of thesolution and the reaction pressure were adjusted and the composition ofthe predicted overhead stream was calculated. The acetate content of thereaction mixture was fixed at 30 kg sodium acetate.

FIG. 3 shows acetate removed as a function of temperature and pressure.The highest levels of acetate are removed at elevated temperature andlow pressure. FIG. 4 shows that MEG losses are highest at elevatedtemperature and reduced pressure. Therefore, an optimumtemperature/pressure condition is required to maximize acetate removalwhile reducing or minimizing MEG losses to acceptable levels.

FIG. 5 plots acetate removal against MEG loss for three temperatures(80, 90 and 100° C.). Lower temperatures and low pressure are preferredto maximize acetate removal. FIG. 6 plots MEG loss as a function ofacetate rejected from the MEG Loop. Using simple blowdown, 950 kg of MEGwill be ejected with every 30 kg of sodium acetate (44 kg MEG per kg ofacetate).

FIG. 7 plots acetate removal as a function of temperature and pressurefor three initial pH conditions: 3.5, 4.5, 5.5). Acetate removalefficiency is increased as the starting solution pH is reduced. For astarting pH of 3.5, 89% of the acetate in the reaction vessel is removedin the overhead stream at 100° C. and 0.1 bara compared to 48.3% for aninitial solution pH of 4.5 and 8.8% for an initial solution pH of 5.5.

Using the acidification/vaporization scheme practiced according to thisinvention can significantly reduce this MEG loss. At 80° C. and 0.15bar, the simulation software predicts 73.8 kg of MEG in the overheadstream along with 8.75 kg of acetic acid (8.58 kg MEG per kg acetate).At 80° C. and 0.15 bar only 40% of the acetate is removed per batch withthe acetate remaining in the liquid phase being routed back to thereclaimer for re-processing.

Experimental Results

The apparatus used in the test is shown in FIG. 8. A double skinned 5Lglass reactor vessel 101—fitted with a pH probe 102 (a Hamilton PolilytePlus ARC 425), a dissolved oxygen probe 103 (Hamilton Oxygold G ARC425), a redox probe 104 (Hamilton Polilyte Plus ORP ARC 425), anelectrical conductivity probe 105 (Hamilton Conducell 4USF ARC PG425),and a stirrer 106—was heated by means of a hot oil circulator bath andheater 107. (Although probes 103, 104 and 105 were fitted to the reactorvessel 101, those probes were not used to collect data during theexperiments.) The reactor vessel 101 was connected to a condenser 108and a distillate collection vessel 109. The reactor vessel 101,condenser 108, and distillate collection vessel 109 were evacuated usinga vacuum pump 110, a pressure control valve 111 and a pressuretransducer 112. An oxygen-free nitrogen supply 113 was connected to thereactor vessel 101 to provide gas blanketing function.

A MEG-water-acetic acid solution was prepared in the reactor vessel 101by adding 93 g of acetic acid (99-100% ex Sigma-Aldrich) to a mixture ofmonoethyleneglycol (1,737 g, Uninhibited CoolFlow MEG ex HydraTechnologies Limited, Fforestfach, Swansea SA5 4AJ, UK) and de-ionisedwater (1,710 g). The pH of this solution was measured as 2.61 at 23° C.The acetate content of the solution was calculated as 2.58 wt %.

The pH of the test mixture was elevated to 10.2 by addition of 100 g ofanhydrous sodium carbonate (ex Sigma-Aldrich) and 1 g of sodiumhydroxide pellets (ex Sigma-Aldrich). At this high pH, the acetic acidis converted to sodium acetate which is non-volatile and which would notbe removed from the reaction vessel by elevating the temperature andreducing the operating pressure.

In conventional MEG loops the organic acids in the formation water andcondensed water are usually present as the sodium salt:

2CH₃CO₂H(aq)+Na₂CO₃(aq)→2CH₃CO₂Na+CO₂(aq)+H₂O

CH₃CO₂H(aq)+NaOH(aq)→CH₃CO₂Na+H₂O

In order to effectively remove the dissolved acetate the pH of thesolution was reduced from 10.2 to 3.5 by addition of 70 g of 37 wt %hydrochloric acid solution (Sigma-Aldrich). The pressure in the reactorvessel 101 was reduced to 0.15 barA and the temperature was raised to80° C. The reactor vessel 101 was held at 0.15 barA/80° C. forapproximately 3.3 hours.

The reactor vessel 101 was allowed to cool and the residue in the vessel101 and the distillate collected in the MEG-water collection vessel 109were weighed and analyzed. The results are shown in Table 1 below.

Table 1 shows that the MEG level in the reactor vessel 101 rises from53.6 wt % to 93.7 wt % as the water component is removed in preferenceto the less volatile MEG at low pressure and elevated temperatures.Table 1 also shows that the acetate component in the reactor vessel 101is also removed in preference to the MEG component and that the acetatecontent of the distillate (predominantly water) is higher (29,093 mg/L)than in the original reactor mixture (measured at 20,994 mg/L,calculated from starting composition at 25,396 mg/L).

TABLE 1 Analysis of Reactor and Distillate Vessel Contents EstimatedAcetate Acetate Inven- MEG by GC Density by IC Calculated tory [Note 1][Note 2] [Note 3] [Note 4] (g) (wt %) (g/L) (mg/L) (g) Reactor @ 3,78153.6 1,065 20,964 75.49 t = 0 Reactor @ 2,079 93.7 1,109 17,326 32.75 t= 3.33 hrs Distillate @ 1,580 6.7 1,006 29,093 45.69 t = 3.33 hrs [Note1]: MEG content measured by Gas Chromatography [Note 2]: Densityestimated as a function of MEG:water:dissolved salt at 20° C. [Note 3]:Acetate content measured using Ion Chromatography [Note 4]: Acetate(g) =Acetate (mg/L) × Inventory (g)/Density (g/L)

Based on a total final acetate measurement of 78.44 g (32.75 g remainingin the reactor vessel 101 plus 45.69 g collected in the distillate), itis calculated that 58.3% in the acetate present as sodium acetate in thereactor vessel at pH=10.2 was removed as acetic acid by reducing pH to3.5 then reducing the pressure to 0.15-0.17 barA and raising thetemperature to 80° C.

Experimental results and predicted values from the OLI STREAM ANALYZER™are shown in Table 2, below. The OLI model predicts 70% removal ofacetate at 80° C./1.5 barA.

TABLE 2 Experimental acetate removal compared with simulated resultsACETATE pH TEMP PRESSURE REMOVED — degC. barA % OLI Prediction 3.50 800.15 70.0 Experimental 3.34-3.78 66-80 0.14-0.17 58.3

SUMMARY

The above preferred embodiments of a system and method made and practiceaccording to this invention are not all possible embodiments. The claimslisted below define the scope of the invention, including equivalents tothe elements listed.

What is claimed:
 1. A process for removal of organic carboxylates from amono ethylene glycol (“MEG”) stream, the system comprising: routing aMEG stream having organic carboxylates in solution to a reaction vessel;acidifying the MEG stream during its residence time within the reactionvessel to a pH no less than about 2.0, the organic carboxylatesremaining in solution as carboxylic acid; and removing in a vapor phasea carboxylic acid-rich overhead stream from the reaction vessel.
 2. Theprocess according to claim 1 further including the step of cooling theMEG stream being routed to the reaction vessel.
 3. The process accordingto claim 1 further including the step of diluting the MEG stream beingrouted to the reaction vessel.
 4. The process according to claim 1further including the steps of cooling and diluting the MEG stream beingrouted to the reaction vessel to a lower % wt MEG and a lowertemperature than an upstream % wt MEG and temperature of the MEG stream.5. The process according to claim 1 wherein the MEG stream also includescalcium and wherein the reaction vessel includes an acetate removal modeand a calcium removal mode, the process further comprising the step ofalternating the reaction vessel between the above mentioned modes, thepressure of the reaction vessel being greater during the calcium removalmode than during the acetate removal mode.
 6. The process according toclaim 1 wherein the reaction vessel is located downstream of a calciumremoval vessel within a MEG recycle loop, the process further comprisinga step of routing a bottom stream from the calcium removal vessel to thereaction vessel.
 7. The process according to claim 1 further comprisinga step of raising the alkalinity of the MEG stream prior to itsresidence time within the reaction vessel.
 8. The process according toclaim 4 wherein the raising alkalinity of said MEG stream step includesadding at least one of sodium carbonate, potassium carbonate, sodiumhydroxide, and potassium hydroxide.
 9. The process according to claim 1wherein the MEG stream also includes calcium and further comprising thestep of removing a calcium-rich bottom stream from the reaction vessel.10. The process according to claim 1 wherein the reaction vessel is at apressure in a range of 0.1 to 0.3 bar.
 11. The process according toclaim 1 wherein the pH is not greater than about 6.0.
 12. The processaccording to claim 1 wherein the acidifying step includes the additionof hydrochloric acid.
 13. The process according to claim 1 wherein thelower % wt MEG is below 80 wt % MEG.
 14. The process according to claim13 wherein the lower % wt MEG is about 50 wt % MEG.
 15. The processaccording to claim 2 wherein the lower temperature is a temperature in arange of 80° to 100° C.
 16. The process according to claim 4 wherein thecooling and diluting the MEG stream step includes water.
 17. The processaccording to claim 4 wherein the acidification of the cooled and dilutedMEG stream occurs under a vacuum.
 18. A process for removal of organiccarboxylates from a mono ethylene glycol (“MEG”) stream, the processcomprising: acidifying the MEG stream during its residence time within areaction vessel, the MEG stream having organic carboxylates including atleast organic acetates in solution and a lower wt % MEG and a lowertemperature within the reaction vessel than upstream of the reactionvessel, the organic acetates remaining in solution during the residencetime as acetic acid, the acidifying step resulting in the MEG streamhaving a pH in a range of about 3.0 to about 6.0; and removing when invapor phase said acetic acid in a carboxylate-rich overhead stream fromthe reaction vessel.
 19. The process of claim 18 wherein theacidification of the MEG stream occurs under sub-ambient pressure. 20.The process according to claim 19 wherein the sub-ambient pressure is apressure in a range of 0.1 to 0.3 bar.
 21. The process according toclaim 18 wherein the acidifying step includes hydrochloric acid.
 22. Theprocess according to claim 18 wherein the lower wt % MEG is below 80 wt% MEG.
 23. The process according to claim 18 wherein the lower wt % MEGis about 50 wt % MEG.
 24. The process according to claim 18 wherein thelower temperature is in a range of 80° to 100° C.
 25. A process forremoval of organic carboxylates and calcium from a mono ethylene glycol(“MEG”) stream, the system comprising: routing the MEG stream to areaction vessel; raising the alkalinity of the MEG stream to convertsaid organic carboxylates to carboxylate salt in solution and saidcalcium to calcium carbonate in solution; removing said calciumcarbonate from the reaction vessel; acidifying the MEG stream in thereaction vessel to a pH no less than 2.0, the carboxylate salt beingconverted to carboxylic acid; and, removing said carboxylic acid fromthe reaction vessel.
 26. The process of claim 25 wherein solids areprecipitated from the MEG stream after raising the alkalinity and theprocess includes the further step of removing said solids.
 27. Theprocess of claim 25 wherein the raising the alkalinity of the MEG streamstep and the removing said calcium carbonate step occur prior to theacidifying of the MEG stream step and removing said carboxylic acidstep.
 28. The process of claim 25 wherein the acidifying of the MEGstream step and removing said carboxylic acid step occur prior to theraising the alkalinity of the MEG stream step and the removing saidcalcium carbonate step.
 29. The process of claim 25 wherein the pH isnot greater than 6.0
 30. The process according to claim 21 wherein thereaction vessel is at a pressure in a range of between about 0.1 bar andabout 0.3 bar.